Substituted N-aryl nitrogen-containing heterocyclic compounds

ABSTRACT

The invention relates to novel substituted N-aryl nitrogen-containing heterocyclic compounds of the general formula (I) ##STR1## and to the compounds isomeric to the substituted N-aryl nitrogen-containing heterocyclic compounds of the formula (I), of the formulae (Ia) and (Ib) ##STR2## in which Q 1 , Q 2 , R 1 , R 2  and Ar have the meanings given in the description, processes for their preparation and their use as herbicides.

This application is a divisional of application Ser. No. 08/849,966,filed on Jun. 6, 1997 (now pending), which is a 371 of PCT/EP95/04759,filed on Dec. 4, 1995.

The invention relates to novel substituted N-aryl nitrogen-containingheterocyclic compounds, processes for their preparation and their use asherbicides.

It is known that certain N-aryl nitrogen-containing heterocycliccompounds have herbicidal properties (cf EP 11693, DE 2952685, DE3026739, U.S. Pat. No. 4,276,420, U.S. Pat. No. 4,326,878, WO 94/14817).However, the compounds known from the patent applications mentioned havenot acquired noteworthy importance.

The novel substituted N-aryl nitrogen-containing heterocyclic compoundsof the general formula (I) ##STR3## in which

Q¹ represents oxygen or sulfur,

Q² represents oxygen or sulfur,

R¹ represents hydrogen, cyano or formyl or represents alkyl which isoptionally substituted by halogen, cyano, carboxyl, alkoxy, alkenyloxy,alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl,alkenyloxycarbonyl or alkinyloxycarbonyl,

R¹ furthermore represents alkenyl or alkinyl, in each case optionallysubstituted by halogen,

R¹ furthermore represents alkylcarbonyl, alkenylcarbonyl,alkinylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl oralkinyloxycarbonyl, in each case optionally substituted by halogen,

R¹ furthermore represents cycloalkyl or cycloalkylcarbonyl, in each caseoptionally substituted by halogen, cyano or carboxyl,

R² represents hydrogen, cyano or formyl, or represents alkyl which isoptionally substituted by halogen, cyano, carboxyl, alkoxy, alkenyloxy,alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl,alkenyloxycarbonyl or alkinyloxycarbonyl,

R² furthermore represents alkenyl or alkinyl, in each case optionallysubstituted by halogen,

R² furthermore represents alkylcarbonyl, alkenylcarbonyl,alkinylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl oralkinyloxycarbonyl, in each case optionally substituted by halogen,

R² furthermore represents cycloalkyl or cycloalkylcarbonyl, in each caseoptionally substituted by halogen, cyano or carboxyl, and

Ar represents the substituted monocyclic or bicyclic aryl or heteroarylgrouping defined below. ##STR4## in which

R³ represents hydrogen or halogen,

R⁴ represents hydrogen or halogen,

R⁵ represents cyano, carboxyl, chlorocarbonyl, carbamoyl, thiocarbamoyl,hydroxyl or halogen, or represents alkyl, alkoxy or alkoxycarbonyl, ineach case optionally substituted by halogen,

R⁶ represents the following grouping

    --A.sup.1 --A.sup.2 --A.sup.3

in which

A¹ represents a single bond, or represents oxygen, sulfur, --SO--, --SO₂--, --CO-- or the grouping --N--A⁴ --, in which A⁴ represents hydrogen,hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylcarbonyl,arylcarbonyl, alkylsulfonyl or arylsulfonyl,

A¹ furthermore represents alkanediyl, alkenediyl, azaalkenediyl,alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, in each caseoptionally substituted by halogen,

A² represents a single bond, or represents oxygen, sulfur, --SO--, --SO₂--, --CO-- or the grouping --N--A⁴ --, in which A⁴ represents hydrogen,hydroxyl, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl,

A² furthermore represents alkanediyl, alkenediyl, azaalkenediyl,alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, in each caseoptionally substituted by halogen,

A³ represents hydrogen, with the proviso that in this case A¹ and/or A²do(es) not represent any single bond,

A³ furthermore represents hydroxyl, mercapto, amino, cyano, isocyano,thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo,chlorosulfonyl or halogen, or represents alkyl, alkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonylor dialkoxy(thio)-phosphoryl, in each case optionally substituted byhalogen or alkoxy,

A³ furthermore represents alkenyl, alkenyloxy, alkenylthio,alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy,alkinylthio, alkinylamino or alkinyloxycarbonyl, in each case optionallysubstituted by halogen,

A³ furthermore represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl,cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl orcycloalkylalkoxycarbonyl, in each case optionally substituted byhalogen, cyano, carboxyl, alkyl and/or alkoxy-carbonyl,

A³ furthermore represents aryl, aryloxy, aralkyl, arylalkoxy,aryloxycarbonyl or arylalkoxycarbonyl, in each case optionallysubstituted by nitro, cyano, carboxyl, halogen, alkyl, halogenalkyl,alkyloxy, halogenalkyloxy and/or alkoxy-carbonyl,

A³ furthermore represents in each case optionally completely or partlyhydrogenated pyrrolyl, pyrrolyl, imidazolyl, triazolyl, furyl, oxiranyl,oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl,isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl,triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, oxazolylalkyl,isoxazolylalkyl, thiazolylalkyl, pyridinylalkyl, pyrimidinylalkyl,pyrazolylalkoxy or furylalkoxy, or represents perhydropyranylalkoxy orpyridylalkoxy, and

R⁷ represents hydrogen or halogen,

or in each case two adjacent radicals--R³ and R⁴, R⁴ and R⁵, R⁵ and R⁶or R⁶ and R⁷ --together represent one of the following groupings

--Q³ --CQ⁴ --, --Q³ --CQ⁴ --Q⁵ --, --Q³ --C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸,R⁹)--Q³ --CQ⁴ --, --Q³--C(R⁸,R⁹)--C(R⁸,R⁹)--, --Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --, --Q³ --C(R⁸)═C(R⁸)--, --C(R⁸)═C(R⁸)--CQ⁴--, --Q³ --C(R⁸,R⁹)--CQ⁴ ----N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸)═N--, --Q³--CQ⁴ --C(R⁸,R⁹)--, --Q³ --CQ⁴ --N(R¹⁰)--, --Q³ --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --C(R⁸,R⁹)--Q³ --CQ⁴ --N(R¹⁰)--,--C(R⁸,R⁹)--C(R⁸,R⁹)--N(R¹⁰)--, --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--,--C(R⁸)═C(R⁸)--N(R¹⁰)--, --C(R⁸)═C(R⁸)--CQ⁴ --N(R¹⁰)--, --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--, --C(R⁸)═N--N(R¹⁰)--,--Q³ C--Q⁴ --C(R⁸,R⁹)--N(R¹⁰)--, Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--

in which

Q³, Q⁴ and Q⁵ are identical or different and in each case representoxygen or sulfur,

R⁸ and R⁹ are identical or different and individually representhydrogen, halogen or alkyl or together represent alkanediyl, and

R¹⁰ represents hydrogen or hydroxyl, or represents alkyl, alkylcarbonyl,alkoxycarbonyl or alkylsulfonyl which are optionally substituted bycyano, halogen, alkoxy, alkyl-carbonyl or alkoxy-carbonyl, or representsalkenyl or alkinyl, in each case optionally substituted by halogen, orrepresents cycloalkyl or cycloalkylalkyl, in each case optionallysubstituted by halogen or alkyl, or represents alkoxy or alkenyloxy, ineach case optionally substituted by halogen, or represents arylalkyl orarylalkoxy, in each case optionally substituted by cyano, halogen,alkyl, halogenoalkyl, alkoxy or halogenoalkoxy,

have now been found, the already known compounds4-(3,4-dichlorophenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one and4-(4-chloro-3-trifluoromethylphenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one(cf DE 2952685 and DE 3026739) being excluded by disclaimer.

The compounds isomeric to the substituted N-aryl nitrogen-containingheterocyclic compounds of the formula (1), of the formulae (Ia) and (Ib)##STR5## in which

Q¹, Q², R¹, R² and Ar have the abovementioned meanings, have furthermorealso been found.

The novel substituted N-aryl nitrogen-containing heterocyclic compoundsof the general formula (I) and, where appropriate, the compounds of theformulae (Ia) or (Ib) are obtained when

(a) (thio)semicarbazide derivatives of the general formula (II) ##STR6##in which

Q¹, Q², R¹, R² and Ar have the abovementioned meanings and

R represents alkyl,

are subjected to a cyclizing condensation reaction, if appropriate inthe presence of a reaction auxiliary and if appropriate in the presenceof a diluent, and thereafter, if appropriate, electrophilic ornucleophilic substitution reactions are carried out in the customarymanner in the context of the definition of the substituents,

or when

(b) aryliminoheterocyclic compounds of the general formula (III)##STR7## in which

Q¹, Q², R¹, R² and Ar have the abovementioned meanings,--or compounds ofthe formula (Ia) or (Ib)--above--

are isomerized thermally ("pyrolytically"), if appropriate in thepresence of a reaction auxiliary and if appropriate in the presence of adiluent.

The compounds of the formula (I) can in principle also be synthesized asshown schematically below:

(c) reaction of aryl iso(thio)cyanates of the formula (IV) withhydrazines of the formula (V) to give aryl(thio)semicarbazides of theformula (VI) and reaction thereof with (thio)phosgene: ##STR8##

(d) reaction of aryl iso(thio)cyanates of the formula (IV) withS-allyldithiocarbazates of the formula (VII) and subsequent cyclizingcondensation: ##STR9##

(e) reaction of N,N-bis-chlorocarbonyl- orN,N-bis-phenoxycarbonyl-arylamines of the formula (VI) --Y:Cl or OC₆ H₅--with hydrazines of the formula (V): ##STR10##

(f) reaction of arylamines of the formula (IX) with hydraziedicarboxylicacid esters of the formula (X): ##STR11##

The compounds of the general formula (I) can also be converted intoother compounds of the general formula (I) according to the abovedefinition by further customary methods, for example by customaryconversions of carboxylic acid groupings or derivatives thereof (forexample R⁵ : COOH→COCl, COOH→COOCH₃, COCl→CONH₂, COOCH₃ →CONH₂, CONH₂→CN, CN→CSNH₂, by alkylation reactions (for example R¹ : H→CH₃ or CHF₂)or by oxidation or sulfurization (for example Q¹ : O→S or S→O)--cf alsothe preparation examples.

The novel substituted N-aryl nitrogen-containing heterocyclic compoundsof the general formula (I) are distinguished by a potent herbicidalactivity.

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, alkenyl or alkinyl, are in each case straight-chain orbranched.

Halogen in general represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine, in particular fluorine orchlorine.

The invention preferably relates to compounds of the formulae (I), (Ia)and (Ib) in which

Q¹ represents oxygen or sulfur,

Q² represents oxygen or sulfur,

R¹ represents hydrogen, cyano or formyl, or represents C₁ -C₆ -alklyl,in each case optionally substituted by fluorine, chlorine, cyano,carboxyl, C₁ -C₄ -alkoxy, C₃ --C₄ -alkenyloxy, C₃ -C₄ -alkinyloxy,C_(1-C) ₄ -alkylthio, C₃ -C₄ -alkenylthio, C₃ -C₄ -alkinylthio, C₁ -C₄-alkoxy-carbonyl, C₃ -C₄ -alkenyloxy-carbonyl or C₃ -C₄-alkinyloxy-carbonyl,

R¹ furthermore represents C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl, in eachcase optionally substituted by fluorine or chlorine,

R¹ furthermore represents C₁ -C₆ -alkenyl or C₃ -C₆ -alkenyl-carbonyl,C₃ -C₆ -alkinyl-carbonyl, C₁ -C₆ -alkoxy-carbonyl, C₃ -C₆-alkenyloxy-carbonyl or C₃ -C₆ -alkinyloxy-carbonyl, in each caseoptionally substituted by fluorine or chlorine,

R¹ furthermore represents C₃ -C₆ -cycloalkyl or C₃ -C₆ -cycloalkylcarbonyl, in each case optionally substituted by fluorine, chlorine,bromine, cyano or carboxyl,

R² represents hydrogen cyano or formyl or represents C₁ -C₆ -alkyl, ineach case optionally substituted by fluorine, chlorine, cyano, carboxyl,C₁ -C₄ -alkoxy C₃ -C₄ -alkenyloxy, C₃ -C₄ -alkinyloxy, C₁ -C₄-alkylthio, C₃ -C₄ -alkenylthio, C₃ -C₄ -alkinylthio, C₁ -C₄--alkoxy-carbonyl, C₃ -C₄ -alkenyloxy-carbonyl or C₃ -C₄-alkinyloxy-carbonyl,

R² furthermore represents C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl, in eachcase optionally substituted by fluorine or chlorine,

R² furthermore represents C₁ -C₆ -alkyl-carbonyl, C₃ -C₆-alkenyl-carbonyl, C₃ -C₆ -alkinyl-carbonyl, C₁ -C₆ -alkoxy-carbonyl, C₃-C₆ -alkenyloxy-carbonyl or C₃ -C₆ -alkinyloxy-carbonyl, in each caseoptionally substituted by fluorine or chlorine,

R² furthermore represents C₃ -C₆ -cycloalkyl or C₃ -C₆-cycloalkyl-carbonyl, in each case optionally substituted by fluorine,chlorine, bromine, cyano or carboxyl, and

Ar represents the substituted monocyclic or bicyclic aryl or heteroarylgrouping defined below ##STR12## in which

R³ represents hydrogen, fluorine, chlorine or bromine,

R⁴ represents hydrogen, fluorine, chlorine or bromine,

R⁵ represents cyano, carboxyl, chlorocarbonyl, carbamoyl, thiocarbamoyl,hydroxyl, fluorine, chlorine, bromine or represents alkyl, alkoxy oralkoxycarbonyl having in each case up to 4 carbon atoms and in each caseoptionally substituted by fluorine and/or chlorine,

R⁶ represents the following grouping

    --A.sup.1 --A.sup.2 --A.sup.3

in which

A¹ represents a single bond, or represents oxygen, sulfur, --SO--, --SO₂--, --CO-- or the grouping --N--A⁴ --, in which A⁴ represents hydrogen,hydroxyl, C₁ -C₄ --alkyl, C₃ -C₄ ---alkenyl, C₃ -C₄ ---alkinyl, C₁ -C₄--alkoxy, phenyl, C₁ -C₄ ---alkyl-carbonyl, phenylcarbonyl, C₁ -C₄---alkyl-sulfonyl or phenylsulfonyl,

A¹ furthermore represents C₁ -C₆ -alkanediyl, C₂ -C₆ -alkenediyl, C₂ -C₆-azaalkenediyl, C₂ -C₆ -alkinediyl, C₃ -C₆ -cycloalkanediyl, C₃ -C₆-cycloalkenediyl or phenylene, in each case optionally substituted byfluorine, chlorine or bromine,

A² represents a single bond, or represents oxygen, --SO--, --SO₂ --,--CO-- or the grouping --N--A⁴ --, in which A⁴ represents hydrogen,hydroxyl, C₁ -C₄ -alklyl, C₁ -C₄ -alkoxy, phenyl, C₁ -C₄ -alkylsulfonylor phenylsulfonyl,

A² furthermore represents C₁ -C₆ -alkanediyl, C₂ -C₆ -alkenediyl, C₂ -C₆-azaalkenediyl, C₂ -C₆ -alkinediyl, C₃ -C₆ -cycloalkanediyl, C₃ -C₆-cycloalkenediyl or phenylene, in each case optionally substituted byfluorine, chlorine or bromine,

A³ represents hydrogen, with the proviso that in this case A¹ and/or A²do(es) not represent a single bond,

A³ furthermore represents hydroxyl, mercapto, amino, cyano, isocyano,thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo,chlorosulfonyl, fluorine, chlorine or bromine,

A³ furthermore represents alkyl alkoxy, alkylsulfinyl, alkylsulfonyl,alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphorylhaving in each case 1to 6 carbon atoms in the alkyl groups and in eachcase optionally substituted by fluorine, chlorine or C₁ -C₄ -alkoxy,

A³ furthermore represents alkenyl, alkenyloxy, alkenylamino,alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino oralkinyloxycarbonyl having in each case 2 to 6 carbon atoms in thealkenyl, alkylidene or alkinyl groups and in each case optionallysubstituted by fluorine or chlorine,

A³ furthermore represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl,cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl orcycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in thecycloalkyl groups and where appropriate 1 to 4 carbon atoms in the alkylgroups and in each case optionally substituted by fluorine, chlorine,cyano, carboxyl, C₁ -C₄ -alkyl and/or C₁ -C₄ -alkoxy-carbonyl,

A³ furthermore represents phenyl phenyloxy, phenyl-C₁ -C₄ -alkyl,phenyl-C₁ -C₄ -alkoxy, phenyloxycarbonyl or phenyl-C₁ -C₄-alkoxycarbonyl, in each case optionally substituted by nitro, cyano,carbonyl, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄-halogenalkyl, C₁ -C₄ -alkyloxy, C₁ -C₄ -halogenalkyloxy and/or C₁ -C₄-alkoxy-carbonyl,

A³ furthermore represents in each case optionally completely or partlyhydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,pyrimidinyl, triazinyl, pyrazolyl-C₁ -C₄ -alkyl, furyl-C₁ -C₄ -alkyl,thienyl-C₁ -C₄ -alkyl, oxazolyl-C₁ -C₄ -alkyl, isoxazolyl-C₁ -C₄ -alkyl,thiazolyl-C₁ -C₄ -alkyl, pyridinyl-C₁ -C₄ -alkyl, pyrimidinyl-C₁ -C₄-alkyl, pyrazolylmethoxy or furylmethoxy, or representsperhydropyranylmethoxy or pyridylmethoxy, and

R⁷ represents hydrogen, fluorine or chlorine,

or in each case two adjacent radicals--R³ and R⁴, R⁴ and R⁵, R⁵ and R⁶or R⁶ and R⁷ --together represent one of the following groupings

--Q³ --CQ⁴ --, --Q³ --CQ⁴ --Q⁵ --, --Q³ --C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸,R⁹)--Q³ --CQ⁴ --, --Q³--C(R⁸,R⁹)--C(R⁸,R⁹)--, --Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --, --Q³ --C(R⁸)═C(R⁸)--, --C(R⁸)═C(R⁸)--CQ⁴--, --Q³ --C(R⁸,R⁹)--CQ⁴ ----N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸)═N--, --Q³--CQ⁴ --C(R⁸,R⁹)--, --Q³ --CQ⁴ --N(R¹⁰)--, --Q³ --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --C(R⁸,R⁹)--Q³ --CQ⁴ --N(R¹⁰)--,--C(R⁸,R⁹)--C(R⁸,R⁹)--N(R¹⁰)--, --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--,--C(R⁸)═C(R⁸)--N(R¹⁰)--, --C(R⁸)═C(R⁸)--CQ⁴ --N(R¹⁰)--, --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--, --C(R⁸)═N--N(R¹⁰)--,--Q³ CQ⁴ --C(R⁸,R⁹)--N(R¹⁰)--, Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--

in which

Q³, Q⁴ Q⁵ are identical or different and in each case represent oxygenor sulfur,

R⁸ and R⁹ are identical or different and individually represent oxygen,fluorine, chlorine, bromine or C₁ -C₄ -alkyl or together represent C₂-C₅ -alkanediyl, and

R¹⁰ represents hydrogen or hydroxyl, or represents alkyl, alkylcarbonyl,alkoxycarbonyl or alkylsulfonyl having in each case 1 to 6 carbon atomsin the alkyl groups and in each case optionally substituted by cyano,fluorine, chlorine, C₁ -C₄ -alkoxy, C₁ -C₄ -alkyl-carbonyl or C₁ -C₄-alkoxy-carbonyl,

R¹⁰ furthermore represents alkenyl or alkinyl having in each case 2 to 6carbon atoms and in each case optionally substituted by fluorine,chlorine or bromine,

R¹⁰ furthermore represents cycloalkyl or cycloalkylalkyl having in eachcase 3 to 6 carbon atoms in the cycloalkyl groups and where appropriate1 to 3 atoms in the alkyl group and in each case optionally substitutedby fluorine, chlorine, bromine or C₁ -C₄ -alkyl,

R₁₀ furthermore represents alkoxy or alkenyloxy having in each case upto 6 carbon atoms and in each case optionally substituted by fluorineand/or chlorine, and

R¹⁰ furthermore represents benzyl or benzyloxy, in each case optionallysubstituted by cyano, fluorine, chlorine, C₁ -C₄ -alkyl, C₁ -C₄-halogenoalkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -halogenoalkoxy,

the already known compounds4-(3,4-dichlorophenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-oneand4-(4-chloro-3-trifluoromethyl-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one(cf DE 2952685 and DE 3026739) being excluded by disclaimer.

The invention particularly relates to compounds of the formulae (I),(Ia) and (Ib) in which

Q¹ represents oxygen or sulfur,

Q² represents oxygen or sulfur,

R¹ represents hydrogen, cyano or formyl, or represents methyl, ethyl, n-or i-propyl or n-, i-, s- or t-butyl, in each case optionallysubstituted by fluorine, chlorine, cyano, carboxyl, methoxy or ethoxy,

R¹ furthermore represents propenyl, butenyl, propinyl or butinyl, ineach case optionally substituted by fluorine or chlorine,

R¹ furthermore represents acetyl, propionyl, methoxycarbonyl orethoxycarbonyl, in each case optionally substituted by fluorine orchlorine,

R¹ furthermore represents cyclopropyl which is optionally substituted byfluorine or chlorine,

R² represents hydrogen, cyano or formyl or represents methyl, ethyl, n-or i-propyl or n-, i-, s- or t-butyl, in each case optionallysubstituted by fluorine, chlorine, cyano, carboxyl, methoxy or ethoxy,

R² furthermore represents propenyl, butenyl, propinyl or butinyl, ineach case optionally substituted by fluorine or chlorine,

R² furthermore represents acetyl, propionyl, methoxycarbonyl orethoxycarbonyl, in each case optionally substituted by fluorine orchlorine,

R² furthermore represents cyclopropyl which is optionally substituted byfluorine or chlorine, and

Ar represents the substituted monocyclic or bicyclic aryl or heteroarylgrouping defined below ##STR13## in which

R³ represents hydrogen, fluorine or chlorine,

R⁴ represents hydrogen, fluorine or chlorine,

R⁵ represents cyano, thiocarbamoyl, chlorine, bromine, methyl,trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy,

R⁶ represents the following grouping

    --A.sup.1 --A.sup.2 --A.sup.3

in which

A¹ represents a single bond, or represents oxygen, sulfur, --SO--, --SO₂--, --CO-- or the grouping --N--A⁴ --, in which A⁴ represents hydrogen,hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- ori-propoxy, methylsulfonyl or ethylsulfonyl,

A¹ furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl,propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2,-diyl,propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl orpropine-1,3-diyl,

A² represents a single bond, or represents oxygen, sulfur, --SO--, --SO₂--, --CO-- or the grouping --N--A⁴ --, in which A⁴ represents oxygen,hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- ori-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl orphenylsulfonyl,

A² furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl,propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl,propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl orpropine-1,3-diyl,

A³ represents hydrogen, with the proviso that in this case A¹ and/or A²do(es) not represent a single bond,

A³ furthermore represents hydroxyl, amino, cyano, nitro, carboxyl,carbamoyl, sulfo, fluorine, chlorine or bromine,

A³ furthermore represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-,i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n-or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl,ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n-or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-,i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl,ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl,diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, ineach case optionally substituted by fluorine, chlorine, methoxy orethoxy,

A³ furthermore represents propenyl, butenyl, propenyloxy, butenyloxy,propenylamino, butenylamino, propylidenamino, butylidenamino,propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy,butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl orbutinyloxycarbonyl, in each case optionally substituted by fluorine orchlorine,

A³ furthermore represents cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,cyclohexylmethyl, cyclopropylmethoxy, cyclo-butylmethoxy,cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylidenamino,cyclohexylidenamino, cyclopentyloxy carbonyl, cyclohexyloxycarbonyl,cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, in each caseoptionally substituted by fluorine, chlorine, cyano, carboxyl, methyl,ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl,

A³ furthermore represents phenyl, phenyloxy, benzyl, phenylethyl,benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, in each caseoptionally substituted by nitro, cyano, carboxyl, fluorine, chlorine,bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy,ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy,methoxycarbonyl and/or ethoxycarbonyl,

A³ furthermore represents in each case optionally completely or partlyhydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl,oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl,thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl,furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl,thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy,furylmethoxy or pyridylmethoxy,

R⁷ represents hydrogen, fluorine or chlorine,

or in each case two adjacent radicals --R³ and R⁴, R⁴ and R⁵, R⁵ and R⁶or R⁶ and R⁷ --together represent one of the following groupings

--Q³ --CQ⁴ --, --Q³ --CQ⁴ --Q⁵ --, --Q³ --C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸,R⁹)--Q³ --CQ⁴ --, --Q³--C(R⁸,R⁹)--C(R⁸,R⁹)--, --Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--Q⁵ --,--C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --, --Q³ --C(R⁸)═C(R⁸)--, --C(R⁸)═C(R⁸)--CQ⁴--, --Q³ --C(R⁸,R⁹)--CQ⁴ --, --N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --, --C(R⁸)═N--,--Q³ --CQ⁴ --C(R⁸,R⁹)--, --Q³ --CQ⁴ --N(R¹⁰)--, --Q³ --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --C(R⁸,R⁹)--Q³ --CQ⁴ --N(R¹⁰)--,--C(R⁸,R⁹)--C(R⁸,R⁹)--N(R¹⁰)--, --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--,--C(R⁸)═C(R⁸)--N(R¹⁰)--, --C(R⁸)═C(R⁸)--CQ⁴ --N(R¹⁰)--, --C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--, --N(R¹⁰)--C(R⁸,R⁹)--CQ⁴ --N(R¹⁰)--, --C(R⁸)═N--N(R¹⁰)--,--Q³ C--Q⁴ --C(R⁸,R⁹)--N(R¹⁰)--, Q³ --C(R⁸,R⁹)--C(R⁸,R⁹)--CQ⁴--N(R¹⁰)--,

in which

Q³, Q⁴ and Q⁵ are identical or different and in each case representoxygen or sulfur,

R⁸ and R⁹ are identical or different and individually representhydrogen, fluorine, chlorine, methyl or ethyl, or together representethane-1,2-diyl (dimethylene), and

R¹⁰ represents hydrogen or hydroxyl, or represents methyl, ethyl, n- ori-propyl or n-, i-, s- or t-butyl which are optionally substituted bycyano, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl,methoxycarbonyl or ethoxy. carbonyl,

R¹⁰ furthermore represents propenyl, butenyl, propinyl or butinyl, ineach case optionally substituted by fluorine, chlorine or bromine,

R¹⁰ furthermore represents cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclohexylmethyl, in each case optionally substituted by fluorine,chlorine, bromine, methyl or ethyl,

R¹⁰ furthermore represents methoxy, ethoxy, n- or i-propoxy, n-, i- ors-butoxy, propenyloxy or butenyloxy, in each case optionally substitutedby fluorine and/or chlorine, and

R¹⁰ furthermore represents benzyl or benzyloxy, in each case optionallysubstituted by cyano, fluorine, chlorine, methyl, ethyl,trifluoromethyl, methoxy, ethoxy, difluoromethyl or trifluoromethoxy,

the already known compounds4-(3,4-dichloro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-oneand4-(4-chloro-3-trifluoromethyl-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one(cf. DE 2952685 and DE 3026739) being excluded by disclaimer.

The abovementioned definitions of radicals given generally or inpreferred ranges apply both to the end products of the formula (I) andalso correspondingly to the starting substances or intermediate productsin each case required for the preparation. These definitions of radicalscan be combined with one another as desired, tat is to say also betweenthe stated ranges of preferred compounds.

Examples of the compounds of the formula (I) according to the inventionare given in the following groups.

Group 1 ##STR14##

Ar here has, for example, the meanings listed below:

2,4-dichlorophenyl, 3-chloro-4-fluoro-phenyl, 2-chloro-4-cyano-phenyl,2-fluoro-4-cyano-phenyl, 4,5-difluorophenyl, 2,4,5-trichloro-phenyl,2,4-dichloro-5-fluoro-phenyl, 2-chloro-4,5-difluoro-phenyl,4-chloro-2,5-di-fluoro-phenyl, 5-chloro-2,4-difluoro-phenyl,2-fluoro-5-chloro cyano-phenyl, 2,4,5-trifluoro-phenyl,2,5-dichloro-4-cyano-phenyl, 2-chloro-5-fluoro-4-cyano-phenyl,2-chloro-4,5-dicyano-phenyl, 2-chloro-4-fluoro-5-cyano-phenyl,2,5-difluoro-4-cyano-phenyl, 4-cyano-3-methyl-phenyl,2-chloro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methoxy-phenyl,2,4-dichloro-5-ethoxy-phenyl, 2,4-dichloro-5-n-propoxy-phenyl,2,4-dichloro-5-i-propoxy-phenyl, 4-chloro-2-fluoro-5-methoxy-phenyl,4-chloro-2-fluoro-5-ethoxy-phenyl, 4-chloro-2-fluoro-5-n-propoxy-phenyl,4-chloro-2-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methyl-phenyl,2,4-dichloro-5-methyl-phenyl, 2-chloro-4-cyano-5-trifluoromethyl-phenyl,4-fluoro-3-trifluoromethyl-phenyl,2-fluoro-4-cyano-5-trifluoromethyl-phenyl,2-chloro-4-methyl-5-trifluoromethyl-phenyl,2-chloro-5-fluoro-4-methoxy-phenyl, 2-fluoro-4-methoxy-5-methyl-phenyl,2,5-difluoro-4-thicarbamoyl-phenyl,2-chloro-4-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methoxy-phenyl,2-fluoro-4-cyano-5-i-propoxy-phenyl,2-chloro-4-cyano-5-(2-propinyloxy)-phenyl,2-fluoro-4-cyano-5-(1-methyl-2-propinyloxy)-phenyl,2-fluoro-4-chloro-5-(1-methyl-2-propinyloxy)-phenyl,2-chloro-4-thio-carbamoyl-5-i-propoxy-phenyl,2-fluoro-4-cyano-5-(2-propenyloxy)-phenyl,2-fluoro-4-chloro-5-(2-propenyloxy)-phenyl,2-chloro-4-cyano-5-methyl-sulfonylamino-phenyl,2-fluoro-4-cyano-5-ethylsulfonylamino-phenyl,2-fluoro-4-thiocarbamoyl-5-methylsulfonylamino-phenyl,2-chloro-4-cyano-5-ethylsulfonylamino-phenyl,2-fluoro-4-cyano-5-cyclopropylsulfonylamino-phenyl,2-fluoro-4-cyano-5-i-propylsulfonylamino-phenyl,2-chloro-4-thiocarbamoyl-5-ethylsulfonylaminophenyl,2-chloro-4-cyano-5-cyanamino-phenyl,2-fluoro-4-cyano-5-(2,2-difluoroethylsulfonylamino)-phenyl,2-fluoro-4-cyano-5-phenyl-sulfonylamino-phenyl,2-fluoro-4-cyano-5-t-butylsulfonylamino-phenyl,2-chloro-4-cyano-5-methoxycarbonyl-phenyl,2-fluoro-4-cyano-5-ethoxycarbonyl-phenyl,2-fluoro-4-chloro-5-ethoxycarbonyl-phenyl,2-fluoro-4-thiocarbamoyl-5-methoxy-carbonyl-phenyl,2-chloro-4-cyano-5-(N-cyclopropyl-ethylsulfonylamino)-phenyl,2-fluoro-4-cyano-5-(1-methyl-2-propinylthio)-phenyl,2-fluoro-4-cyano-5-methylaminophenyl,2-chloro-4-thiocarbamoyl-5-methoxycarbonylmethyl-phenyl,2-chloro-4-cyano-5-(N-methyl-ethylsulfonylamino)-phenyl,2-fluoro-4-cyano-5-i-propoxycarbonyl-phenyl,2-fluoro-4-chloro-5-i-propoxycarbonyl-phenyl,2-fluoro-4-cyano-5-(bis-ethylsulfonyl-aminophenyl,2-fluoro-4-cyano-5-(N-methylsulfonyl-ethylsulfonylamino)-phenyl,2-fluoro-4-cyano-5-(1-methoxycarbonyl-ethoxy)-phenyl,2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethoxy)-phenyl,2-fluoro-4-chloro-5-(1-methoxycarbonyl-ethoxy)-phenyl,2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethoxy)-phenyl,2-fluoro-4-cyano-5-cyclopropyloxy-phenyl,2-chloro-4-cyano-5-dimethylamino-phenyl,2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-phenyl,4-chloro-2-fluoro-5-tetrahydrofurylmethoxy-phenyl,2-fluoro-4-cyano-5-amino-phenyl,2-fluoro-4-cyano-5-methylaminocarbonyl-phenyl,2-fluoro-4-cyano-5-methylsulfonyloxy-phenyl,2-chloro-4-cyano-5-difluoromethoxy-phenyl,2-fluoro-4-chloro-5-methoxycarbonylmethoxy-phenyl,2-fluoro-4-chloro-5-ethoxycarbonyl-methoxy-phenyl,2-fluoro-4-cyano-5-methoxycarbonylmethoxy-phenyl,2-fluoro-4-cyano-5-ethoxycarbonylmethoxy-phenyl,4-cyano-3-(1-methyl-2-propinyloxy)-phenyl,2-fluoro-4-cyano-5-dimethyl-aminocarbonyl-phenyl,2-fluoro-4-cyano-5-cyanomethoxy-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl,2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-nitro-phenyl,2-fluor0-4-cyano-5-diethoxyphosphorylamino-phenyl,2-fluoro-4-cyano-5-chlorosulfonyl-phenyl,2-fluoro-4-cyano-5-formylamino-phenyl,2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl,2-fluoro-4-cyano-5-diethoxyphosphorylmethoxy-phenyl,4-chloro-2-fluoro-5-diethoxy-phosphorylmethoxy-phenyl,2-fluoro-4-cyano-5-(1-diethoxyphosphorylethoxy)-phenyl,4-chloro-2-fluoro-5-(1-diethoxyphosphoryl-ethoxy)-phenyl,2-chloro-4-cyano-5-hydroxy-phenyl,2-fluoro-4-cyano-5-(N,N-diacetyl-amino)-phenyl,2-fluoro-4-cyano-5-acetylamino-phenyl,2-chloro-4-cyano-5-thiocyanato-phenyl,2-fluoro-4-cyano-5-diethylaminooxy-phenyl,2-fluoro-4-cyano-5-tetrahydrofuryloxy-phenyl,2-fluoro-4-cyano-5-ureido-phenyl,2-fluoro-4-cyano-5-dimethoxymethylenamino-phenyl,2-chloro-4-cyano-5-ethoxymethylenamino-phenyl,2-fluoro-4-cyano-5-(2-chloro-ethoxycarbonyl-oxy)-phenyl,2-chloro-4-cyano-5-dimethylaminomethlylenamino-phenyl,2-chloro-4-cyano-5-(perhydropyran-4-yloxy)-phenyl,2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethyl)-phenyl,4-chloro-2-fluoro-5-(2-methoxycarbonyl-ethyl)-phenyl,2-chloro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-chloro-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-bromo-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-bromo-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2,3-dibromo-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2,3-dibromo-2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-s-butoxycarbonyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(1,2-dibromo-2-methoxycarbonyl-ethyl)_phenyl,2-chloro-4-cyano-5-(2-chloro-2-i-propoxy-carbonyl-ethyl)-phenyl,2,4-dichloro-5-(2-methoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-ethylamino-carbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethenyl)-phenyl,2-fluoro-4-chloro-5-(2-methoxycarbonyl-ethenyl)-phenyl,2-fluoro-4-cyano-5-(2-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-ethoxycarbonyl-ethenyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-cyclopropylamino-carbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-dimethylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-dichloro-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(2-carboxy-ethenyl)-phenyl,2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-ethenyl)-phenyl,2,6-difluoro-4-cyano-5-i-propoxy-phenyl,2-chloro-2-fluoro-4-cyano-6-fluoro-3-i-propoxy-phenyl,2-chloro-6-fluoro-3-i-propoxy-4-trifluoromethyl-phenyl,2,6-di-chloro-4-cyano-3-fluoro-phenyl,2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl,2-chloro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl,2-chloro-4-cyano-5-carboxy-phenyl,2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethyl)-phenyl,2-fluoro-4-chloro-5-(1-i-propoxycarbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-i-butoxy-phenyl), 2-chloro-4-cyano-5-i-butoxy-phenyl,2-chloro-4-cyano-5-(2-methoxy-ethoxy)-phenyl,2-fluoro-4-chloro-5-(2-methoxy-ethoxy)-phenyl,2-fluoro-4-chloro-5-i-butoxy-phenyl, 4-hydroxy-4-ethoxycarbonyl-phenyl,2-fluoro-4-cyano-5-i-propoxycarbonyl-phenyl,2-fluoro-4-hydroxy-5-i-propoxycarbonyl-phenyl,2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl,2-fluoro-4-cyano-5-(2-oxetanyloxy-carbonylmethoxy)-phenyl,2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl,2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl,4-chloro-2-fluoro-5-(2-chloro-2-propenyloxy)-phenyl,2-fluoro-4-chloro-5-methoxycarbonylmethylthio-phenyl,2-fluoro-4-chloro-5-ethoxycarbonylmethylthio-phenyl,2-fluoro-4-cyano-5-methoxycarbonylmethylthio-phenyl,2-fluoro-4-cyano-5-ethoxycarbonylmethylthio-phenyl,2-fluoro-4-chloro-5-(1-methoxycarbonyl-ethylthio)-phenyl,2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethylthio)-phenyl,2-fluoro-4-cyano-5-(1-methoxycarbonyl-ethylthio)-phenyl,2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethylthio)-phenyl, ##STR15##

R here represents, for example, hydrogen, hydroxyl, methyl, ethyl, n- ori-propyl, i- or s-butyl, allyl, propargyl, methoxy, ethoxy, n- ori-propoxy, cyanomethyl, carboxymethyl, methoxymethyl, ethoxymethyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, acetyl, propionyl,methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfonyl.

Group 2 ##STR16##

Ar here has, for example, the meanings listed above in Group 1.

Group 3 ##STR17##

Ar here has, for example, the meanings listed above in Group 1.

Group 4 ##STR18##

Ar here has, for example, the meanings listed above in Group 1.

Group 5 ##STR19##

Ar here has, for example, the meanings listed above in Group 1.

Group 6 ##STR20##

Ar here has, for example, the meanings listed above in Group 1.

Group 7 ##STR21##

Ar here has, for example, the meanings listed above in Group 1.

Group 8 ##STR22##

Ar here has, for example, the meanings listed above in Group 1.

Group 9 ##STR23##

Ar here has, for example, the meanings listed above in Group 1.

Group 10 ##STR24##

Ar here has, for example, the meanings listed above in Group 1.

Group 11 ##STR25##

Ar here has, for example, the meanings listed above in Group 1.

Group 12 ##STR26##

Ar here has, for example, the meanings listed above in Group 1.

Group 13 ##STR27##

Ar here has, for example, the meanings listed above in Group 1.

Group 14 ##STR28##

Ar here has, for example, the meanings listed above in Group 1.

Group 15 ##STR29##

Ar here has, for example, the meanings listed above in Group 1.

Group 16 ##STR30##

Ar here has, for example, the meanings listed above in Group 1.

Group 17 ##STR31##

Ar here has, for example, the meanings listed above in Group 1.

Group 18 ##STR32##

Ar here has, for example, the meanings listed above in Group 1.

Group 19 ##STR33##

Ar here has, for example, the meanings listed above in Group 1.

Group 20 ##STR34##

Ar here has, for example, the meanings listed above in Group 1.

Group 21 ##STR35##

Ar here has, for example, the meanings listed above in Group 1.

Group 22 ##STR36##

Ar here has, for example, the meanings listed above in Group 1.

Group 23 ##STR37##

Ar here has, for example, the meanings listed above in Group 1.

Group 24 ##STR38##

Ar here has, for example, the meanings listed above in Group 1.

Group 25 ##STR39##

Ar here has, for example, the meanings listed above in Group 1.

Group 26 ##STR40##

Ar here has, for example, the meanings listed above in Group 1.

Group 27 ##STR41##

Ar here has, for example, the meanings listed above in Group 1.

Group 28 ##STR42##

Ar here has, for example, the meanings listed above in Group 1.

Group 29 ##STR43##

Ar here has, for example, the meanings listed above in Group 1.

Group 30 ##STR44##

Ar here has, for example, the meanings listed above in Group 1.

Group 31 ##STR45##

Ar here has, for example, the meanings listed above in Group 1.

Group 32 ##STR46##

Ar here has, for example, the meanings listed above in Group 1.

Group 33 ##STR47##

Ar here has, for example, the meanings listed above in Group 1.

Group 34 ##STR48##

Ar here has, for example, the meanings listed above in Group 1.

Group 35 ##STR49##

Ar here has, for example, the meanings listed above in Group 1.

Group 36 ##STR50##

Ar here has, for example, the meanings listed above in Group 1.

Group 37 ##STR51##

Ar here has, for example, the meanings listed above in Group 1.

Group 38 ##STR52##

Ar here has, for example, the meanings listed above in Group 1.

Group 39 ##STR53##

Ar here has, for example, the meanings listed above in Group 1.

Group 40 ##STR54##

Ar here has, for example, the meanings listed above in Group 1.

Group 41 ##STR55##

Ar here has, for example, the meanings listed above in Group 1.

Group 42 ##STR56##

Ar here has, for example, the meanings listed above in Group 1.

Group 43 ##STR57##

Ar here has, for example, the meanings listed above in Group 1.

Group 44 ##STR58##

Ar here has, for example, the meanings listed above in Group 1.

Group 45 ##STR59##

Ar here has, for example, the meanings listed above in Group 1.

Group 46 ##STR60##

Ar here has, for example, the meanings listed above in Group 1.

Group 47 ##STR61##

Ar here has, for example, the meanings listed above in Group 1.

Group 48 ##STR62##

Ar here has, for example, the meanings listed above in Group 1.

Group 49 ##STR63##

Ar here has, for example, the meanings listed above in Group 1.

Group 50 ##STR64##

Ar here has, for example, the meanings listed above in Group 1.

Group 51 ##STR65##

Ar here has, for example, the meanings listed above in Group 1.

Group 52 ##STR66##

Ar here has, for example, the meanings listed above in Group 1.

Group 53 ##STR67##

Ar here has, for example, the meanings listed above in Group 1.

Group 54 ##STR68##

Ar here has, for example, the meanings listed above in Group 1.

Group 55 ##STR69##

Ar here has, for example, the meanings listed above in Group 1.

Group 56 ##STR70##

Ar here has, for example, the meanings listed above in Group 1.

Group 57 ##STR71##

Ar here has, for example, the meanings listed above in Group 1.

Group 58 ##STR72##

Ar here has, for example, the meanings listed above in Group 1.

Group 59 ##STR73##

Ar here has, for example, the meanings listed above in Group 1.

Group 60 ##STR74##

Ar here has, for example, the meanings listed above in Group 1.

Group 61 ##STR75##

Ar here has, for example, the meanings listed above in Group 1.

Group 62 ##STR76##

Ar here has, for example, the meanings listed above in Group 1.

Group 63 ##STR77##

Ar here has, for example, the meanings listed above in Group 1.

Group 64 ##STR78##

Ar here has, for example, the meanings listed above in Group 1.

Group 65 ##STR79##

Ar here has, for example, the meanings listed above in Group 1.

Group 66 ##STR80##

Ar here has, for example, the meanings listed above in Group 1.

Group 67 ##STR81##

Ar here has, for example, the meanings listed above in Group 1.

Group 68 ##STR82##

Ar here has, for example, the meanings listed above in Group 1.

Group 69 ##STR83##

Ar here has, for example, the meanings listed above in Group 1.

Group 70 ##STR84##

Ar here has, for example, the meanings listed above in Group 1.

Group 71 ##STR85##

Ar here has, for example, the meanings listed above in Group 1.

Group 72 ##STR86##

Ar here has, for example, the meanings listed above in Group 1.

Group 73 ##STR87##

Ar here has, for example, the meanings listed above in Group 1.

Group 74 ##STR88##

Ar here has, for example, the meanings listed above in Group 1.

Group 75 ##STR89##

Ar here has, for example, the meanings listed above in Group 1.

If, for example,4-(4-cyano-2,5-difluoro-phenyl)-1-methoxycarbonylthiosemicarbazide isused as the starting substance, the course of the reaction in process(a) according to the invention can be represented by the followingequation: ##STR90##

If for example,2-(4-chloro-2-fluoro-5-methoxy-phenylimino)-3,4-dimethyl-3,4-dihydro-5-oxo-1,3,4-thiadiazoleis used as the starting substance, the course of the reaction in process(b) according to the invention can be outlined by the followingequation: ##STR91##

Formula (II) provides a general definition of the (thio)semicarbazidederivatives to be used as starting substances in process (a) accordingto the invention for the preparation of the compounds of the generalformula (I). In formula (II), Q¹, Q², R¹, R² and Ar preferably or inparticular have those meanings which have already been mentioned aboveas preferred or as particularly preferred for Q¹, Q², R¹, R² and Ar inconnection with the description of the compounds of the formula (I); Rpreferably represents alkyl having 1-4 carbon atoms, in particularmethyl or ethyl.

The starting substances of the formula (II) are known and/or can beprepared by known processes (cf. Synthesis 1982, 159-160; DE 1200824, DE2952685 and DE 3026739).

The (thio)semicarbazide derivatives of the formula (II) are obtainedwhen

(α) aryl iso(thio)cyanates of the general formula (IV)

    Ar--N═C═Q.sup.1                                    (IV)

in which

Ar and Q¹ have the abovementioned meanings,

are reacted with carbazates of the general formula (XI)

    RO--CQ.sup.2 --N(R.sup.2)--NH--R.sup.1                     (XI)

in which

Q², R¹ and R² have the abovementioned meanings and

R represents alkyl, and preferably represents C₁ -C₆ -alkyl, andparticularly preferably represents methyl or ethyl,

if appropriate in the presence of a diluent, such as, for example,toluene, at temperatures of between 0° C. and 150° C. (cf thepreparation examples),

or when

(β) arylamines of the general formula (XII)

    Ar--NH.sub.2                                               (XII)

in which

Ar has the abovementioned meaning,

are reacted with (thio)carbonyl-diimidazole of the formula (XIII)

    Im--CQ.sup.1 --Im                                          (XIII)

in which

Q¹ has the abovementioned meaning and

Im represents imidazolyl,

and with carbazates of the general formula (XI)

    RO--CQ.sup.2 --N(R.sup.2)--NH--R.sup.1                     (XI)

in which

Q², R¹ and R² have the abovementioned meanings and

R represents alkyl, and preferably represents C₁ -C₆ -alkyl, andparticularly preferably represents methyl or ethyl,

if appropriate in the presence of a reaction auxiliary, such as, forexample, potassium hydroxide, and if appropriate in the presence of adiluent, such as, for example, methanol, ethanol and/or water, attemperatures of between 0° C. and 100° C.

The aryl iso(thio)cyanates of the formula (IV) required as precursorsare known and/or can be prepared by known processes (cf. DE 4327743, DE4335438 and DE 4343451).

The carbazates of the formula (VIII) furthermore required as precursorsare known organic chemicals.

Process (a) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Possible reaction auxiliariesare all the customary organic or inorganic bases. These include, forexample, alkali metal or alkaline earth metal hydrides, hydroxides,amides, alcoholates, acetates, carbonates or hydrogencarbonates, suchas, for example, lithium, sodium, potassium or calcium hydride, lithium,sodium or potassium amide, sodium or potassium methylate, sodium orpotassium ethylate, sodium or potassium propylate, aluminumisopropylate, sodium or potassium tert-butylate, sodium or potassiumhydroxide, ammonium hydroxide, sodium, potassium or calcium acetate,ammonium acetate, sodium, potassium, rubidium, cesium, magnesium orcalcium carbonate, ammonium carbonate and sodium or potassiumhydrogencarbonate, and basic organic nitrogen compounds, such astrimethylamine, triethylamine, tripropylamine, tributylamine,ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine,ethyl-dicyclohexylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine,pyridine, 2-methyl-, 3-methyl- and 4-methyl-pyridine, 2,4-dimethyl-,2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine,5-ethyl-2-methyl-pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane, (DABCO),diazabicyclononene (DBN or diazabicycloundecene (DBU).

Possible diluents for carrying out process (a) according to theinvention are the customary organic solvents. These include, inparticular, aliphatic, alicyclic or aromatic, optionally halogenatedhydrocarbons, such as, for example, pentane, hexane, heptane, petroleumether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene,dichlorobenzene, cyclohexane, methylcyclohexane, methylene chloride,chloroform or carbon tetrachloride; ethers, such as diethyl ether,diisopropyl ether, t-butyl methyl ether, t-pentyl methyl ether, dioxane,tetrahydrofuran, ethylene glycol dimethyl or diethyl ether or diethyleneglycol dimethyl or diethyl ether; ketones, such as acetone, butanone ormethyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile,butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide,N-methylformanilide, N-methyl-pyrrolidone orhexamethylphosphoric acid triamide; esters, such as methyl, ethyl, n- ori-propyl or n-, i- or s-butyl acetate; sulfoxides, such as dimethylsulfoxide; alcohols, such as methanol, ethanol, n- or i-propanol, n-,i-, s- or t-butanol, ethylene glycol monomethyl or monoethyl ether,diethylene glycol monomethyl ether or diethylene glycol monoethyl ether;and mixtures thereof with water or pure water.

The reaction temperatures can be varied within a substantial range whencarrying out process (a) according to the invention. The process is ingeneral carried out at temperatures of between 0° C. and +150° C.,preferably at temperatures between 10° C. and 120° C.

Process (a) according to the invention is in general carried out undernormal pressure. However, it is also possible to carry out the processunder increased or reduced pressure--in general between 0.1 bar and 10bar.

For carrying out process (a) according to the invention, the startingsubstances of formula (II) are in general initially introduced into thereaction vessel in a suitable diluent and--if appropriate after additionof a reaction auxiliary--are stirred at the required temperature untilthe reaction has ended. Working up can be carried out in the customarymanner (cf the preparation examples).

Formula (III) provides a general definition of the aryliminoheterocycliccompounds to be used as starting substances in process (b) according tothe invention for the preparation of the compounds of the generalformula (I). In formula (III), Q¹, Q², R¹, R² and Ar preferably or inparticular have those meanings which have already been mentioned aboveas preferred or as particularly preferred for Q¹, Q², R¹, R² and Ar inconnection with the description of the compounds of the formula (I).

The starting substances of the formula (III) are not yet known from theliterature; however, they are the subject of a prior application whichhas not previously been published (cf. DE 4424787).

The aryliminoheterocyclic compounds of the formula (III) are obtainedwhen aryl(thio)semicarbazides of the general formula (VI) are reactedwith reactive carbonic acid derivatives, such as, for example, phosgeneor thiophosgene, if appropriate in the presence of diluents, such as,for example, toluene and/or methylene chloride, at temperatures ofbetween 0° and 100° C.

Formulae (Ia) and (Ib) provide general definitions of the compounds tobe used, if appropriate, as starting substances, in process (b)according to the invention for the preparation of the compounds of thegeneral formula (I). In formulae (Ia) and (Ib), Q¹, Q², R¹, R² and Arpreferably or in particular have those meanings which have already beenmentioned above as preferred or as particularly preferred for Q¹, Q²,R¹, R² and Ar in connection with the description of the compounds of theformula

The compounds of the formula (Ia) or (Ib) are obtained when N-arylnitrogen-containing heterocyclic compounds of the general formula (I) inwhich at least one of the groups R¹ or R² represents hydrogen arereacted with acylating or acylating agents of the formulae (IXa or (IXb)

    X--R.sup.1                                                 (XIVa)

    X--R.sup.2                                                 (XIVb)

in which

R¹ and R² have the abovementioned meanings, with the exception ofhydrogen, and

X represents halogen--preferably chlorine, bromine or iodine--or one ofthe groupings --SO₂ --O--R¹ or --O--SO₂ --O--R²,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary at temperatures of between 0° C. and80° C. (cf. the preparation examples).

The same diluents and reaction auxiliaries as in process (a) accordingto the invention are preferably possible here.

If appropriate, process (b) according to the invention is carried out inthe presence of a reaction auxiliary. The same reaction auxiliaries asin process (a) according to the invention, but furthermore in additionalso alkali metal sulfides, such as, for example, sodium sulfide orpotassium sulfide, are possible here.

Process (b) according to the invention is preferably carried out using adiluent. The same diluents as in process (a) according to the inventionare possible here.

The reaction temperatures can be varied within a substantial range whencarrying out process (b) according to the invention. The process is ingeneral carried out at temperatures of between 0° C. and +250° C.,preferably at temperatures of between 20° C. and 150° C.

Process (b) according to the invention is in general carried out undernormal pressure. However, it is also possible to carry out the processunder increased or reduced pressure--in general between 0.1 bar and 10bar.

For carrying out process (b) according to the invention, the startingsubstances of the formula (III) or of the formulae (Ia) or (Ib)--are ingeneral initially introduced into the reaction vessel in a suitablediluent and are stirred at the required temperature until the reactionhas ended. Working up can be carried out in the customary manner.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Antiemis, Galinsoga, Chenopodium, Urtica, Senecio,Amarantus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, inlawns, turf and pasture-land, and for the selective combating of weedsin annual cultures.

The compounds of the formula (I) according to the invention areparticularly suitable for selectively combating monocotyledon anddicotyledon weeds in monocotyledon cultures both by the pre-emergenceand by the post-emergence method.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobezenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulfoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulfite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuff, suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in the form of their formulations, can also be used asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Suitable herbicides for the mixtures are known herbicides, for exampleanilides such as, for example, diflufenican and propanil; arylcarboxylicacids such as, for example, dichloropicolinic acid, dicamba andpicloram; amyloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoicesters such as, for example, diclofop-methyl, fenoxaprop-ethyl,fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones suchas, for example, chloridazon and norflurazon; carbamates such as, forexample, chlorpropham, desmedipham, phenmedipham and propham;chloroacetanilides such as, for example, alachlor, acetochlor,butachlor, metazachlor, metolachlor, pretilachlor and propachlor,dinitroanilines such as, for example, oryzalin, pendimethalin andtrifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox,fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureassuch as, for example, chlortoluron, diuron, fluometuron, isoproturon,linuron and methabenzthiazuron; hydroxylamines such as, for example,alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim;imidazolinones such as, for example, imazethapyr, imazamethabenz,imazapyr and imazaquin; nitriles such as, for example, bromoxynil,dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet;sulfonylureas such as, for example, amidosulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-metyl,nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyland tibenuron-methyl; thiocarbamates such as, for example, butylate,cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb,thiobencarb and tri-allate; triazines such as, for example, atrazine,cyanazine, simazine, simetryne, terbutryne and terbutylazine;triazinones such as, for example, hexazinone, metamitron and metribuzin;others such as, for example, aminotriazole, benfuresate, bentazone,cinmetlylin, clomazone, clopyralid, difenzo-quat, dithiopyr,ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben,pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellants, plant nutrientsand agents for improving soil structure is also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 1 g and 10 kg of active compound perhectare of soil surface, preferably between 5 g and 5 kg per ha

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR92##

20.2 g (75 mmol) of4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxycarbonyl-semicarbazide arestirred in 50 ml of 25% strength aqueous potassium hydroxide solution at80° C. for 2 hours. After the mixture has been cooled to 20° C., it isbrought to pH=4 with concentrated hydrochloric acid and the productobtained as crystals is isolated by filtration.

16.0 g (90% of theory) of4-carboxy-2,5-difluorophenyl)-1,2,4-triazoline-2,5-dione of meltingpoint >250° C. are obtained.

Example 2 ##STR93##

A mixture of 3.90 g (10 mmol) of4-(4-cyano-2-fluoro-5-methylsulfonylaminophenyl)-2-methyl-1-ethoxycarbonyl-thiosemicarbazide,8.10g (80 mmol) of triethylamine and 100 ml of acetonitrile is stirred atthe reflux temperature for 12 hours. The solvent is removed in vacuo,the residue is stirred with water, the mixture is acidified withconcentrated hydrochloric acid and the product obtained as crystals isisolated by filtration.

1.20 g (35% of theory) of4-(4-cyano-2-fluoro-5-methylsulfonylaminophenyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-oneof melting point >250° C. are obtained.

Example 3 ##STR94##

A mixture of 5.2 g (15 mmol) of4-(4-chloro-2-fluoro-5-1-propoxycarbonyl-phenyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one,5.2 g (37.5 mmol) of potassium carbonate and 50 ml of acetonitrile isstirred at 60° C. for 60 minutes; Frigen (CHClF₂) is then passed in at60° C. for 6 hours. The mixture is subsequently concentrated underreduced pressure, the residue is taken up in water, the mixture isacidified with concentrated hydrochloric acid and extracted withmethylene chloride, and the organic phase is dried over sodium sulfateand filtered. The filtrate is concentrated and the crude productobtained in the residue is purified by column chromatography (silicagel, hexane/ethyl acetate, Vol.:P 7:1).

0.7 g (12% of theory) of4-chloro-2-fluoro-5-i-propoxycarbonyl-phenyl)-1-methyl-2-difluoromethyl-5-thioxo-1,2,4-triazolin-3-oneof melting point 51° C. is obtained.

Example 4 ##STR95##

A mixture of 7.6 g (23 mmol) of2-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2H)-1,4-bezoxazin-6-yl-imino)-3-methyl-3,4-dihydro-5-oxo-(4H)-1,3,4-thiadiazoleand 20 ml of dimethyl sulfoxide is heated at 50° C. for 2 hours, at 70°C. for a further 2 hours and at 80° C. for a further 2 hours. It is thenconcentrated under reduced pressure, the residue is stirred with waterand the product obtained as crystals is isolated by filtration.

6.6 g (85% of theory) of4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2H)-1,4-benzoxazin-6-yl)-1-metyl-5-thioxo-1,2,4-triazolin-3-oneof melting point 190° C. are obtained.

The compounds of the formula (I) listed in the following Table 1, forexample, can also be prepared analogously to Examples 1 to 4 and inaccordance with the general description of the preparation processesaccording to the invention.

                                      TABLE 1                                     __________________________________________________________________________     ##STR96##                                                                    Examples of the compounds of the formula (I)                                  Example                                      Physical                         No.  Q.sup.1                                                                         Q.sup.2                                                                         R.sup.1   R.sup.2   Ar              data                             __________________________________________________________________________     5   O O H         CH.sub.3                                                                                 ##STR97##      M.p.: 234° C.              6   S O CH.sub.3  H                                                                                        ##STR98##      M.p.: 224° C.              7   S O CH.sub.3  CHO                                                                                      ##STR99##      M.p.: 95° C.               8   O S H         CH.sub.3                                                                                 ##STR100##     M.p.: 172° C.              9   S O CH.sub.3  CHF.sub.2                                                                                ##STR101##     M.p.: 183° C.             10   S O CH.sub.3  CH.sub.3                                                                                 ##STR102##     M.p.: 118° C.             11   S O CH.sub.3  H                                                                                        ##STR103##     M.p.: 139° C.             12   S O CH.sub.3  CH.sub.3                                                                                 ##STR104##     M.p.: 227° C.             13   S S CH.sub.3  CH.sub.3                                                                                 ##STR105##     M.p.: 175° C.             14   S O CH.sub.3  CHF.sub.2                                                                                ##STR106##     M.p.: 122° C.             15   S O CH.sub.3  CHF.sub.2                                                                                ##STR107##     M.p.: 64° C.              16   S S CH.sub.3  CH.sub.3                                                                                 ##STR108##     M.p.: 155° C.             17   S S CH.sub.3  CH.sub.3                                                                                 ##STR109##     M.p.: 70° C.              18   S S CH.sub.3  CH.sub.3                                                                                 ##STR110##     M.p.: 198° C.             19   S S CH.sub.3  CH.sub.3                                                                                 ##STR111##                                      20   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR112##     M.p.: 120° C.             21   S S CH.sub.3  CH.sub.3                                                                                 ##STR113##     M.p.: 228° C.             22   S S CH.sub.3  CH.sub.3                                                                                 ##STR114##     M.p.: 146° C.             23   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR115##     Mp.: 142° C.              24   S S CH.sub.3  CH.sub.3                                                                                 ##STR116##     M.p.: 192° C.             25   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR117##     M.p.: 149° C.             26   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR118##     M.p.: 195° C.             27   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR119##     M.p.: 148° C.             28   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR120##     M.p.: 133° C.             29   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR121##                                      30   S S CH.sub.3  CH.sub.3                                                                                 ##STR122##                                      31   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR123##     M.p.: 197° C.             32   S S CH.sub.3  CH.sub.3                                                                                 ##STR124##     M.p.: 229° C.             33   S S CH.sub.3  CH.sub.3                                                                                 ##STR125##     M.p.: 174° C.             34   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR126##     M.p.: 103° C.             35   S S CH.sub.3  CH.sub.3                                                                                 ##STR127##     M.p.: 259° C.             36   S S C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          ##STR128##     M.p.: 248° C.             37   S S CH.sub.3  CH.sub.3                                                                                 ##STR129##     M.p.: 251° C.             38   O S H         CH.sub.3                                                                                 ##STR130##     M.p.: 201° C.             39   O S CHO       CH.sub.3                                                                                 ##STR131##     M.p.: 75° C.              40   O O CHF.sub.2 CH.sub.3                                                                                 ##STR132##     M.p.: 70° C.              41   O S CH.sub.3  CH.sub.3                                                                                 ##STR133##     M.p.: 157° C.             42   O S CH.sub.3  CH.sub.3                                                                                 ##STR134##     M.p.: 250° C.             43   O S CHF.sub.2 CH.sub.3                                                                                 ##STR135##     M.p.: 127° C.             44   O S CH.sub.3  CH.sub.3                                                                                 ##STR136##     M.p.: 58° C.              45   O S CH.sub.3  CH.sub.3                                                                                 ##STR137##     M.p.: 138° C.             46   O S CH.sub.3  CH.sub.3                                                                                 ##STR138##     M.p.: 236° C.             47   O S                                                                                ##STR139##                                                                             CH.sub.3                                                                                 ##STR140##     M.p.: 122° C.             48   O S                                                                                ##STR141##                                                                             CH.sub.3                                                                                 ##STR142##                                      49   O S --CH.sub.2 CF.sub.3                                                                     CH.sub.3                                                                                 ##STR143##     M.p.: 135° C.             50   O S                                                                                ##STR144##                                                                             CH.sub.3                                                                                 ##STR145##     M.p.: 42° C.              51   O S CH.sub.3  CH.sub.3                                                                                 ##STR146##     M.p.: 163° C.             52   O S CHF.sub.2 CH.sub.3                                                                                 ##STR147##     M.p.: 176° C.             53   O S CH.sub.3  CH.sub.3                                                                                 ##STR148##     M.p.: 150° C.             54   O S H         CH.sub.3                                                                                 ##STR149##     M.p.: 67° C.              55   O S H         H                                                                                        ##STR150##     M.p.: 250° C.             56   O S H         CH.sub.3                                                                                 ##STR151##                                      57   O O                                                                                ##STR152##                                                                              ##STR153##                                                                              ##STR154##     n.sub.d.sup.20  = 1.5442         58   O O                                                                                ##STR155##                                                                              ##STR156##                                                                              ##STR157##     n.sub.d.sup.20  = 1.5349         59   O O                                                                                ##STR158##                                                                             CH.sub.3                                                                                 ##STR159##     n.sub.d.sup.20  = 1.5600         60   O O                                                                                ##STR160##                                                                              ##STR161##                                                                              ##STR162##                                      61   O O H         CH.sub.3                                                                                 ##STR163##     M.p.: 215° C.             62   O O H         CH.sub.3                                                                                 ##STR164##     M.p.: 250° C.             63   O O H         CH.sub.3                                                                                 ##STR165##     M.p.: 156° C.             64   O O H         CH.sub.3                                                                                 ##STR166##     .sup.1 H--NMR  (CDCl.sub.3):                                                  3.25,  4.40-4.46,  7.22-7.24                                                  ppm                              65   O S H         CH.sub.3                                                                                 ##STR167##     M.p.: 210° C.             66   O O H         CH.sub.3                                                                                 ##STR168##     M.p.: 163° C.             67   O S H         CH.sub.3                                                                                 ##STR169##     M.p.: 143° C.             68   O S H         CH.sub.3                                                                                 ##STR170##     M.p.: 158° C.             69   O S H         CH.sub.3                                                                                 ##STR171##     M.p.: 75° C.              70   O S CH.sub.3  CH.sub.3                                                                                 ##STR172##     .sup.1 H--NMR  (CDCl.sub.3):                                                   3.45, 3.73,  7.30-7.40 ppm      71   O S CH.sub.3  CH.sub.3                                                                                 ##STR173##     M.p.: 146° C.             72   O S CH.sub.3  CH.sub.3                                                                                 ##STR174##     M.p.: 208° C.             73   O S CH.sub.3  CH.sub.3                                                                                 ##STR175##     M.p.: 195° C.             74   O O H         CH.sub.3                                                                                 ##STR176##     (amorphous)                      75   O O H         H                                                                                        ##STR177##     M.p.: 150° C.             76   O O CH.sub.3  CH.sub.3                                                                                 ##STR178##     M.p.: 101° C.             77   O S                                                                                ##STR179##                                                                             CH.sub.3                                                                                 ##STR180##     M.p.: 172° C.             78   O S                                                                                ##STR181##                                                                             CH.sub.3                                                                                 ##STR182##     M.p.: 199° C.             79   O S H         CH.sub.3                                                                                 ##STR183##     amorphous                        80   S S CH.sub.3  CH.sub.3                                                                                 ##STR184##     M.p.: 160° C.             81   O S H         CH.sub.3                                                                                 ##STR185##     amorphous                        82   O S CHF.sub.2 CH.sub.3                                                                                 ##STR186##     M.p.: 99° C.              83   O S CH.sub.3  CH.sub.3                                                                                 ##STR187##                                      84   S S CH.sub.3  CH.sub.3                                                                                 ##STR188##     M.p.: 131° C.             85   O S CHF.sub.2 CH.sub.3                                                                                 ##STR189##                                      86   O S C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                 ##STR190##                                      __________________________________________________________________________

The compound listed as Example 13 in Table 1 can be prepared, forexample, as follows: ##STR191##

A mixture of 1.0 g (0.3 mmol) of2-(4-cyano-2-fluoro-4-i-propoxy-phenylimino)-3,4-dihydro-3,4-methyl-5-thioxo(4H)-1,3,4-thiadiazole,0.1 g (0.1 mmol) of sodium sulfide and 20 ml of ethanol is heated underreflux for about 20 hours. It is then concentrated, the residue is takenup in methylene chloride and the mixture is washed with water, driedwith sodium sulfate and filtered. The filtrate is concentrated, theresidue is digested with diethyl ether and the product obtained ascrystals is isolated by filtration.

0.25 g (25% of theory) of4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)-1,2-dimethyl-1,2,4-triazoline-2,5-dithioneof melting point 175° C. is obtained.

The compound listed as Example 21 in Table 1 can be prepared, forexample, as follows: ##STR192##

Hydrogen sulfide is passed into a mixture of 0.9 g (2.6 mmol) of4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)-1,2-dimethyl-1,2,4-triazoline-2,5-dithione,2 ml (14 mmol) of triethylamine and 20 ml of pyridine at 90° C. for 9hours. After the mixture has been cooled, the solvent is stripped off ona rotary evaporator and the residue is stirred with 2 normalhydrochloric acid. The crude product is filtered off with suction,washed with water, dried and purified by column chromatography (mobilephase: hexane/ethyl acetate 4:1).

0.42 g (43% of theory) of4-(2-fluoro-5-i-propoxy-4-thiocarbamoylphenyl)-1,2-dimethyl-1,2,4-triazoline-2,5-dithioneof melting point 228° C. is obtained.

The compound listed as Example 46 in Table 1 can be prepared, forexample, as follows: ##STR193##

A solution of 2.1 g (6 mmol) of4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2H)-1,4-benzoxazin-6-yl)-1-methyl-5-methylthio-1,2,4-triazolin-3-onein 20 ml of dimethylformamide is heated under reflux for 16 hours. It isthen concentrated under a water pump vacuum and the residue is purifiedby column chromatography.

0:9 (43% of theory) of4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2H)-1,4-benzoxazin-6-yl)-1,2-dimethyl-5-thioxo-1,2,4-triazolin-3-oneof melting point 236° C. is obtained

The compound listed as Example 61 in Table 1 can be prepared, forexample, as follows: ##STR194##

44.7 g (0.15 mol) of4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxycarbonyl-2-methyl-semicarbazideare stirred in 200 ml of 4 molar aqueous potassium hydroxide solution at80° C. for 30 minutes. After the mixture has been cooled to 20° C., itis brought to pH=4 with concentrated hydrochloric acid and the productobtained as crystals is isolated by filtration.

36 g (95% of theory) of4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl-1,2,4-triazoline-3,5-dione ofmelting point 215° C. are obtained.

The compound listed as Example 62 in Table 1 can be prepared, forexample, as follows: ##STR195##

27.1 g (0.1 mol) of4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl-1,2,4-triazole-3,5-dione areheated to 80° C. in 200 ml of toluene. 14.3 g (0.12 mol) of thionylchloride are added dropwise at this temperature in the course of 30minutes, and the mixture is heated to the reflux temperature and stirredfor about 2 hours until the evolution of gas has ended. After themixture has been cooled to 20° C., the product obtained as crystals isisolated by filtration.

7.2 g (25% of theory) of4-(4-chlorocarbonyl-2,5-difluoro-phenyl)-1-methyl-1,2,4-triazole-3,5-dioneof melting point >250° C. are obtained.

The compound listed as Example 63 in Table 1 can be prepared, forexample, as follows: ##STR196##

6.5 g (0.024 mol) of4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl-1,2,4-triazole-3,5-dione arestirred at the reflux temperature with 200 ml of methanol and two dropsof sulfuric acid for 8 hours. After the mixture has been cooled to 20°C., it is concentrated under a water pump vacuum, the residue isdissolved in methylene chloride, the solution is washed with water andthe organic phase is dried over sodium sulfate and freed thoroughly fromthe solvent under a water pump vacuum.

4.2 g (62% of theory) of4-4-methoxycarbonyl-2,5-difluoro-phenyl)-1-methyl-1,2,4-triazole-3,5-dioneof melting point 156° C. are obtained.

The compound listed as Example 69 in Table 1 can be prepared, forexample, as follows: ##STR197##

29.3 g (0.096 mol) of4-(4-chloro-2-fluoro-phenyl)-2-methyl-1-ethoxycarbonyl-thiosemicarbazideare stirred at the reflux temperature in 400 ml of acetonitrile with 78g (0.77 mol) of triethylamine for 8 hours and, after the mixture hasbeen cooled, it is concentrated under a water pump vacuum. Water isadded to the residue, the mixture is brought to pH=4 with concentratedhydrochloric acid and extracted with methylene chloride, and the organicphase is separated off, dried over sodium sulfate and concentrated undera water pump vacuum.

22 g (88% of theory) of4-(4-chloro-2-fluoro-phenyl)-1-methyl-5-thioxo-1,2,4-triazol-3-one ofmelting point 75° C. are obtained.

The compound listed as Example 70 in Table 1 can be prepared, forexample, as follows: ##STR198##

7.1 g (0.026 mol) of the meso ionic compound according to Example(Ia-5)--below--are stirred under reflux in 100 ml of dimethylformamidefor 18 hours and, after the mixture has been cooled, it is concentratedunder a water pump vacuum.

5.9 g (83% of theory) of4-(4-chloro-2-fluoro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-oneare obtained.

¹ H-NMR (CDCl₃): 3.45; 3.73; 7.30-7.40 ppm.

The compound listed as Example 71 in Table 1 can be prepared, forexample, as follows: ##STR199##

4.65 g (0.017 mol) of4-(4-chloro-2-fluoro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-oneare initially introduced into the reaction vessel in 30 ml ofconcentrated sulfuric acid, and 3 ml of 98% strength nitric acid areadded dropwise at 0° C. The mixture is subsequently stirred at roomtemperature for 8 hours and stirred with ice water and the product whichhas precipitated out is filtered off.

2.9 g (54% of theory) of4-(4-chloro-2-fluoro-5-nitro-phenyl)-1,2-ethyl-5-thioxo-1,2,4-triazol-3-oneof melting point 146° C. are obtained.

The compound listed as Example 72 in Table 1 can be prepared, forexample, as follows: ##STR200##

2.6 g (0.008 mol) of4-(4-chloro-2-fluoro-5-nitro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-oneare initially introduced into the reaction vessel in 20 ml of aceticacid with 10 ml of water and 10 ml of ethyl acetate, and 4.6 g (0.0082mol) of iron powder are added in portions, the temperature being kept atmaximum of 45° C. using an ice-bath. When the addition has ended, themixture is subsequently stirred at 23° C. for 2 hours and filtered withsuction and the residue is washed with water. The filtrate is extractedwith ethyl acetate and the organic phase is washed with sodiumhydrogencarbonate solution, dried over sodium sulfate and concentratedunder a water pump vacuum.

1.5 g (65% of theory) of4-(4-chloro-2-fluoro-5-amino-phenyl-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-oneof melting point 208° C. are obtained.

The compound listed as Example 73 in Table 1 can be prepared, forexample, as follows: ##STR201##

1.8 g (0.018 mol) of triethylamine and then 2.3 g (0.018 mol) ofethanesulfonyl chloride are added to 1.3 g (0.0045 mol) of4-(4-choro-2-fluoro-5-amino-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-onein 50 ml of methylene chloride at -10° C., the mixture is stirred atroom temperature for 3 hours, water is added and the organic phase isseparated off, dried over sodium sulfate and concentrated under a waterpump vacuum.

2.0 g (94% of theory) of4-[4-chloro-2-fluoro-5-(diethylsulfonyl)-amino-phenyl]-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-oneof melting point 195° C. (decomposition) are obtained.

Compounds of the formulae (Ia) or (Ib):

Example (Ia-1) ##STR202##

A mixture of 4.2 g (12 mmol) of4-(4-chloro-2-fluoro-5-i-propoxycarbonyl-phenyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one,3.5 g (25 mmol) of potassium carbonate, 2.2 g (15 mmol) of methyl iodideand 60 ml of acetonitrile is stirred at 40° C. for 12 hours. It is thenconcentrated, the residue is taken up in water, the mixture is acidifiedwith concentrated hydrochloric acid and extracted with methylenechloride and the organic phase is dried with sodium sulfate andfiltered. The filtrate is concentrated and the crude product obtained asthe residue is purified by column chromatography (silica gel, methylenechloride/methanol, volume: 40:1).

1.0 g (24% of theory) of the compound of the structural formula givenabove of melting point 159° C. is obtained.

The compounds of the formula (Ia) listed in the following Table 2, forexample, can also be prepared analogously.

                                      TABLE 2                                     __________________________________________________________________________     ##STR203##                                                                   Examples of the compounds of the formula (Ia)                                 Example                        Physical                                       No.  Q.sup.1                                                                          Q.sup.2                                                                          R.sup.1                                                                          R.sup.2                                                                          Ar            data                                           __________________________________________________________________________    Ia-2 S  O  CH.sub.3                                                                         CH.sub.3                                                                          ##STR204##   M.p.: 237° C.                           Ia-3 S  O  CH.sub.3                                                                         CH.sub.3                                                                          ##STR205##   M.p.: 168° C.                           Ia-4 S  O  CH.sub.3                                                                         CH.sub.3                                                                          ##STR206##   M.p.: 185° C.                           Ia-5 S  O  CH.sub.3                                                                         CH.sub.3                                                                          ##STR207##   M.p.: 182° C.                           __________________________________________________________________________

The compound listed as Example (Ia-5) in Table 2 can be prepared, forexample, as follows ##STR208##

20.7 g (0.08 mol) of4-(4-chloro-2-fluoro-phenyl)-1-methyl-5-thioxo-1,2,4-triazol-3-one areinitially introduced into the reaction vessel with 150 ml of dimethylsulfoxide and 22 g (0.16 mol) of potassium carbonate. 23 g (0.16 mol) ofmethyl iodide are then added dropwise at 0° C. in the course of 30minutes. The mixture is subsequently stirred at 23° C. for 4 hours andthen concentrated. The residue is stirred with water, the mixture isacidified with concentrated hydrochloric acid and extracted withmethylene chloride, and the organic phase is dried over sodium sulfateand concentrated under a water pump vacuum. After the residue has beenstirred with isopropanol, the product obtained as crystals is isolatedby filtration.

7.8 g (36% of theory) of the mesoionic compound of the structure givenabove are obtained.

Starting substances of the formula (II):

Example (II-1) ##STR209##

18.0 g (0.10 mol) of 4-cyano-2,5-difluoro-phenyl isocyanate are added toa solution of 10.4 g (0.10 mol) of ethyl carbazate in 100 ml of tolueneat 10° C. and the mixture is stirred at 20° C. for 2 hours and then atthe reflux temperature for a further 2 hours. The product obtained ascrystals after cooling is isolated by filtration.

24.2 g (90% of theory) of4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxy-carbonyl-semicarbazide ofmelting point 245° C. are obtained.

Example (II-2) ##STR210##

18.8 g (0.1 mol) of 4-chloro-2-fluoro-phenyl isothiocyanate are stirredat the reflux temperature in 200 ml of acetonitrile with 11.8 g (0.1mol) of 2-methyl-1-ethoxy-carbonyl-hydrazine and 9.24 g (0.11 mol) ofsodium hydrogencarbonate for 8 hours. After the mixture has been cooled,it is concentrated under a water pump vacuum, the residue is stirredwith water, the mixture is extracted with methylene chloride and theorganic phase is separated off, dried over sodium sulfate andconcentrated under a water pump vacuum.

29 g (95% of theory) of 4-(4-chloro-2-fluoro-phenyl)-2-methyl-1-ethoxycarbonyl-thiosemicarbazide of melting point 151° C. are obtained.

Starting substances of the formula (III):

Example (III-1) ##STR211##

6 g (12 mmol) of a 20% strength solution of phosgene in toluene areadded to a suspension of 3.1 g (10 mmol) of2-methyl-4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2HI)-1,4-benzoxazin-6-yl)-thiosemicarbazidein 50 ml of methylene chloride at about 20° C. The reaction mixture isheated at 40° C. for about 15 hours, the solvent is removed in vacuo andthe residue is taken up in water. The mixture is neutralized with sodiumbicarbonate solution and the solid is filtered off, washed with waterand dried in vacuo at 40-50° C.

2.8 g (84% of theory) of2-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl-(2H)-1,4-benzoxazin-6-yl-imino)-3-methyl-3,4-dihydro-5-oxo-(4H)-1,3,4-thiadiazoleare obtained.

Melting point: 214° C.

Example (III-2) ##STR212##

0.66 g (5.7 mmol) of thiophosgene is added to a solution of 1.7 g (5.7mmol) of4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)-1,2-dimethylthiosemicarbazide in30 ml of dry methylene chloride. The reaction is slightly exothermic.The reaction mixture is stirred at the reflux temperature for 4 hours,the solvent is removed in vacuo and the residue is stirred withsaturated sodium carbonate solution. The solid which forms is filteredoff, washed with water and pressed off on clay.

1.5 g (78% of theory) of2-4-cyano-2-fluoro-5-i-propoxy-phenylimino)-3,4-dimethyl-5-thio-1,3,4-thiadiazoleof melting point 117° are obtained.

Starting substances of the formula (IV):

Example (IV-1) ##STR213##

129 g (1.12 mol) of thiophosgene are added to 81 g (0.56 mol) of4-chloro-2-fluoro-aniline in 500 ml of chlorobenzene at 80° C. to 90° C.in the course of 1 hour and the mixture is then stirred at the refluxtemperature for 2 hours until the evolution of gas has ended. The clearsolution is concentrated to dryness under a water pump vacuum.

102 g (97% of theory) of 4-chloro-2-fluoro-phenyl isothiocyanate areobtained

¹ H-NMR (CDCl₃): 7.10-7.20 ppm; GC-MS: (M=187) 98.4%.

USE EXAMPLES Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to preparationexamples 3, 9, 10, 12, 13, 14 and 15, when applied in amounts of 60g/ha, show in some cases a good tolerability toward crop plants, suchas, for example, barley and corn (10-70%) and a very potent actionagainst weeds, such as Alopecurus (90-100%), Cynodon (95-100%), Setaria(70-100%), Amaranthus (90-100%), Chenopodium (100%), Matricaria(95-100%), Polygonum (80-100%), Portulaca (95-100%) and Viola (90-100%).

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. After threeweeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to preparationexamples 3, 4, 9, 10, 12, 13, 14 and 15 and Ia-1 and Ia-2, when appliedin amounts of between 15 and 250 g/ha, show a potent action againstweeds, such as Amaranthus (60-100%), Chenopodium (90-100%), Datura(80-100%), Galium (90-100%) and Veronica (50-100%).

What is claimed is:
 1. A substituted N-aryl nitrogen-containingheterocyclic compound of formula (I) ##STR214## in which Q¹ representsoxygen or sulfur,Q² represents oxygen or sulfur, R¹ represents hydrogen,cyano or formyl, or represents C₁ -C₆ -alkyl, in each case optionallysubstituted by fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₃-C₄ -alkenyloxy, C₃ -C₄ -alkinyloxy, C₁ -C₄ -alkylthio, C₃ -C₄-alkenylthio, C₃ -C₄ -alkinylthio, C₁ -C₄ -alkoxy-carbonyl, C₃ -C₄-alkenyloxy-carbonyl or C₃ -C₄ -alkinyloxy-carbonyl, R¹ furthermorerepresents C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl, in each case optionallysubstituted by fluorine or chlorine, R¹ furthermore represents C₁ -C₆-alkyl-carbonyl, C₃ -C₆ -alkenyl-carbonyl, C₃ -C₆ -alkinyl-carbonyl, C₁-C₆ -alkoxy-carbonyl, C₃ -C₆ -alkenyloxy-carbonyl or C₃ -C₆-alkinyloxy-carbonyl, in each case optionally substituted by fluorine orchlorine, R¹ furthermore represents C₃ -C₆ -cycloalkyl or C₃ -C₆-cycloalkyl-carbonyl, in each case optionally substituted by fluorine,chlorine, bromine, cyano or carboxyl, R² represents hydrogen, cyano orformyl, or represents C₁ -C₆ -alkyl, in each case optionally substitutedby fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₃ -C₄-alkenyloxy, C₃ -C₄ -alkinyloxy, C₁ -C₄ -alkylthio, C₃ -C₄ -alkenylthio,C₃ -C₄ -alkinylthio, C₁ -C₄ -alkoxy-carbonyl, C₃ -C₄-alkenyloxy-carbonyl or C₃ -C₄ -alkinyloxy-carbonyl, R² furthermorerepresents C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl, in each case optionallysubstituted by fluorine or chlorine, R² furthermore represents C₁ -C₆-alkyl-carbonyl, C₃ -C₆ -alkenyl-carbonyl, C₃ -C₆ -alkinyl-carbonyl, C₁-C₆ -alkoxy-carbonyl, C₃ -C₆ -alkenyloxy-carbonyl or C₃ -C₆-alkinyloxy-carbonyl, in each case optionally substituted by fluorine orchlorine, R² furthermore represents C₃ -C₆ -cycloalkyl or C₃ -C₆-cycloalkyl-carbonyl, in each case optionally substituted by fluorine,chlorine, bromine, cyano or carboxyl, and Ar represents ##STR215## inwhich R³ represents hydrogen, fluorine, chlorine or bromine, R⁶represents the following grouping

    --A.sup.1 --A.sup.2 --A.sup.3

in which A¹ represents a single bond, or represents oxygen, sulfur,--SO--, --SO₂ --, --CO-- or the grouping --N--A⁴ --, in which A⁴represents hydrogen, hydroxyl, C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl, C₃ -C₄-alkinyl, C_(1-C) ₄ -alkoxy, phenyl, C₁ -C₄ -alkyl-carbonyl,phenylcarbonyl, C₁ -C₄ -alkyl-sulfonyl or phenylsulfonyl, A¹ furthermorerepresents C₁ -C₆ -alkanediyl, C₂ -C₆ -alkenediyl, C₂ -C₆-azaalkenediyl, C₂ -C₆ -alkinediyl, C₃ -C₆ -cycloalkanediyl, C₃ -C₆-cycloalkenediyl or phenylene, in each case optionally substituted byfluorine, chlorine or bromine, A² represents a single bond, orrepresents oxygen, sulfur, --SO--, --SO₂ --, --CO-- or the grouping--N--A⁴ --, in which A⁴ represents hydrogen, hydroxyl, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, phenyl, C₁ -C₄ -alkylsulfonyl or phenylsulfonyl, A²furthermore represents C₁ -C₆ -alkanediyl, C₂ -C₆ -alkenediyl, C₂ -C₆-azaalkenediyl, C₂ -C₆ -alkinediyl, C₃ -C₆ -cycloalkanediyl, C₃ -C₆-cycloalkenediyl or phenylene, in each case optionally substituted byfluorine, chlorine or bromine, A³ represents hydrogen, with the provisothat in this case A¹ and/or A² do(es) not represent a single bond, A³furthermore represents hydroxyl, mercapto, amino, cyano, isocyano,thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo,chlorosulfonyl, fluorine, chlorine or bromine, A³ furthermore representsalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino,dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in eachcase 1 to 6 carbon atoms in the alkyl groups and in each case optionallysubstituted by fluorine, chlorine or C₁ -C₄ -alkoxy, A³ furthermorerepresents alkenyl, alkenyloxy, alkenylamino, alkylidenamino,alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino oralkinyloxycarbonyl having in each case 2 to 6 carbon atoms in thealkenyl, alkylidene or alkinyl groups and in each case optionallysubstituted by fluorine or chlorine, A³ furthermore representscycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy,cycloalkylidenamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonylhaving in each case 3 to 6 carbon atoms in the cycloalkyl groups andwhere appropriate 1 to 4 carbon atoms in the alkyl groups and in eachcase optionally substituted by fluorine, chlorine, cyano, carboxyl, C₁-C₄ -alkyl and/or C₁ -C₄ -alkoxy-carbonyl, A³ furthermore representsphenyl, phenyloxy, phenyl-C₁ -C₄ -alkyl, phenyl-C₁ -C₄ -alkoxy,phenyloxycarbonyl or phenyl-C₁ -C₄ -alkoxycarbonyl, in each caseoptionally substituted by nitro, cyano, carboxyl, fluorine, chlorine,bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenalkyl, C₁ -C₄ -alkyloxy, C₁ -C₄-halogenalkyloxy and/or C₁ -C₄ -alkoxy-carbonyl, A³ furthermorerepresents in each case optionally completely or partly hydrogenatedpyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl,dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,pyrazolyl-C₁ -C₄ -alkyl, furyl-C₁ -C₄ -alkyl, thienyl-C₁ -C₄ -alkyl,oxazolyl-C₁ -C₄ -alkyl, isoxazolyl-C₁ -C₄ -alkyl, thiazolyl-C₁ -C₄-alkyl, pyridinyl-C₁ -C₄ -alkyl, pyrimidinyl-C₁ -C₄ -alkyl,pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxyor pyridylmethoxy, and R⁷ represents hydrogen, fluorine or chlorine, R⁸and R⁹ are identical or different and individually represent hydrogen,fluorine, chlorine, bromine or C₁ -C₄ -alkyl or together represent C₂-C₅ -alkanediyl, and R¹⁰ represents hydrogen or hydroxyl, or representsalkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl having in eachcase 1 to 6 carbon atoms in the alkyl groups and in each case optionallysubstituted by cyano, fluorine, chlorine, C₁ -C₄ -alkoxy, C₁ -C₄-alkyl-carbonyl or C₁ -C₄ -alkoxy-carbonyl, R¹⁰ furthermore representsalkenyl or alkinyl having in each case 2 to 6 carbon atoms and in eachcase optionally substituted by fluorine, chlorine or bromine, R¹⁰furthermore represents cycloalkyl or cycloalkylalkyl having in each case3 to 6 carbon atoms in the cycloalkyl groups and where appropriate 1 to3 atoms in the alkyl group and in each case optionally substituted byfluorine, chlorine, bromine or C₁ -C₄ -alkyl, R₁₀ furthermore representsalkoxy or alkenyloxy having in each case up to 6 carbon atoms and ineach case optionally substituted by fluorine and/or chlorine, and R¹⁰furthermore represents benzyl or benzyloxy, in each case optionallysubstituted by cyano, fluorine, chlorine, C₁ -C₄ -alkyl, C₁ -C₄-halogenoalkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -halogenoalkoxy.
 2. Asubstituted N-aryl nitrogen-containing heterocyclic compound of formula(I), as claimed in claim 1, in whichQ¹ represents oxygen or sulfur, Q²represents oxygen or sulfur, R¹ represents hydrogen, cyano or formyl, orrepresents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, ineach case optionally substituted by fluorine, chlorine, cyano, carboxyl,methoxy or ethoxy, R¹ furthermore represents propenyl, butenyl, propinylor butinyl, in each case optionally substituted by fluorine or chlorine,R¹ furthermore represents acetyl, propionyl, methoxycarbonyl orethoxycarbonyl, in each case optionally substituted by fluorine orchlorine, R¹ furthermore represents cyclopropyl which is optionallysubstituted by fluorine or chlorine, R² represents hydrogen, cyano orformyl, or represents methyl, ethyl, n- or i-propyl or n-, i-, s- ort-butyl, in each case optionally substituted by fluorine, chlorine,cyano, carboxyl, methoxy or ethoxy, R² furthermore represents propenyl,butenyl, propinyl or butinyl, in each case optionally substituted byfluorine or chlorine, R² furthermore represents acetyl, propionyl,methoxycarbonyl or ethoxycarbonyl, in each case optionally substitutedby fluorine or chlorine, R² furthermore represents cyclopropyl which isoptionally substituted by fluorine or chlorine.
 3. A method of combatingundesirable plants which comprises allowing an effective amount of theN-aryl nitrogen-containing heterocyclic compound of formula (I) asclaimed in claim 1 to act on undesirable plants and/or theirenvironment.
 4. A herbicidal composition which comprises an effectiveamount of a N-aryl nitrogen-containing heterocyclic compound of formula(I) as claimed in claim 1 in combination with a carrier.